EP0573053A1 - Foto- und wärmehärtende Beschichtungszusammensetzung und Verfahren zum Herstellen von Resist-Lötmasken - Google Patents

Foto- und wärmehärtende Beschichtungszusammensetzung und Verfahren zum Herstellen von Resist-Lötmasken Download PDF

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Publication number
EP0573053A1
EP0573053A1 EP93108973A EP93108973A EP0573053A1 EP 0573053 A1 EP0573053 A1 EP 0573053A1 EP 93108973 A EP93108973 A EP 93108973A EP 93108973 A EP93108973 A EP 93108973A EP 0573053 A1 EP0573053 A1 EP 0573053A1
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EP
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Prior art keywords
composition
tertiary amine
epoxy resin
amine compound
water
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EP93108973A
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English (en)
French (fr)
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EP0573053B1 (de
Inventor
Teruo Saitoh
Shinji Nakamura
Norio Kimura
Hitoshi Inagaki
Morio Suzuki
Kenji Sawazaki
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Taiyo Holdings Co Ltd
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Taiyo Ink Mfg Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/285—Permanent coating compositions
    • H05K3/287—Photosensitive compositions

Definitions

  • This invention relates to a novel photo-curable and thermosetting coating composition and more particularly to a coating composition which can be diluted with water and put to use as developed with a dilute aqueous acid solution and, therefore, is useful for the formation of a solder resist pattern on a printed circuit board and suitable especially for the formation of a solder resist pattern on a printed circuit board by means of a spray coater and a curtain coater.
  • This invention further relates to a method for the formation of a solder resist pattern on a printed circuit board by the use of the coating composition mentioned above and to a printed circuit board having a solder resist film formed thereon in a prescribed pattern.
  • the electronic devices have been showing a growing inclination toward reduction in size and weight, improvement in quality, and enrichment of versatility of performance.
  • the printed circuit boards are tending toward increased density of printed circuits and adoption of surface mount technology of the printed circuit board.
  • the photoimageable solder resists which rely on the photographic process for the formation of a resist pattern have been developed.
  • a photo-curable and thermosetting liquid coating composition comprising a resin curable with an activated energy ray, which is obtained by the reaction of a saturated or unsaturated polybasic acid anhydride with a reaction product of a novolak type epoxy compound and an unsaturated monocarboxylic acid, a photopolymerization initiator, a diluent and an epoxy compound is disclosed in published Japanese Patent Application KOKAI (Early Publication) No. 61-243869 and corresponding U.S. Patent No. 5,009,982.
  • this liquid coating composition possesses satisfactory properties as a solder resist, it defies dilution with water and, therefore, must be diluted with a large amount of organic solvent when it is to be applied by the technique of spray coating or curtain coating.
  • an organic solvent is also employed for the cleaning of the jig which has been used for applying the coating composition.
  • the use of organic solvent entails the problems of environmental pollution and fire hazard. Thus, the settlement of such problems is desired.
  • the water-soluble resins generally include the resins which are obtained by neutralizing with an amine such carboxylic group-containing resins as copolymers of acrylic acid with polymerizable monomers, and polyvinyl alcohol, polyethylene glycol, and carboxymethylcellulose, for example.
  • the compositions which use photosensitive resins based on such water-soluble resins as mentioned above are not readily used as solder resists because they fail to acquire the resistance to soldering temperature and the electrical properties which are necessary for a solder resist.
  • the products of neutralization with an amine entail the problem of environmental pollution because they inevitably liberate the amine into the ambient atmosphere when they are thermally cured.
  • solder resists requiring highly reliable resistance to soldering temperature and electrical insulation, therefore, the organic solvent type liquid coating compositions mentioned above have been generally used inevitably.
  • the composition which has as essential components thereof a non-proton type onium salt-containing resin derived from an aromatic epoxy resin compound and a photopolymerization initiator is disclosed in published Japanese Patent Application KOKAI No. 2-1858.
  • this composition is soluble in water, a layer of this composition applied to the substrate surface, even when it is predried at a temperature of 100°C or less, entails the problem of poor tack-free touch of finger due to hygroscopicity.
  • the non-proton type onium salt for the impartation of solubility in water attains thorough thermal decomposition in the step of postcure only with difficulty.
  • the cured coating film consequently obtained retains ionic groups and exhibits inferior electrical insulating property or the like after absorption of moisture.
  • the cation electrodepositing coating material which has as a main component thereof a cationic water-soluble or water-dispersible resin is disclosed in published Japanese Patent Application KOKAI No. 1-279251. Even when this composition is thermally treated, however, it cannot be used as a solder resist because this composition contains no thermosetting component.
  • An object of this invention is to provide a photo-curable and thermosetting coating composition capable of being diluted with water, which produces a solder resist film excelling in various properties required for solder resist such as resistance to soldering temperature, electrical insulating property, resistance to electrolytic corrosion, resistance to chemicals, and tightness of adhesion and which, after being predried, manifests excellence in tack-free touch of finger, developing property, photo-curing property, and shelf life and proves to be ideal in terms of freedom from environmental pollution and fire hazard.
  • Another object of this invention is to provide a method for the formation of a solder resist pattern by the steps of applying the coating composition to a printed circuit board, selectively exposing the applied layer to an actinic ray, developing the coating film with a dilute aqueous acid solution having only a sparing skin-stimulating property thereby forming a resist pattern unlike the conventional method for the formation of a solder resist pattern by the use of a dilute aqueous alkaline solution, and thereafter thermally curing the formed resist film.
  • a further object of this invention is to provide a printed circuit board comprising a solder resist film which is formed thereon in a prescribed pattern and excels in various properties as mentioned above.
  • a photo-curable and thermosetting coating composition which can be diluted and washed with water, characterized by comprising a tertiary amine compound having at least one ethylenically unsaturated bond in the molecule, a photopolymerization initiator, a diluent, and an epoxy resin, said tertiary amine compound being used as neutralized with a carboxylic acid and said epoxy resin being incorporated therein in the proportion of 2 to 15 equivalents per equivalent of said carboxylic acid to be used for said neutralization.
  • a method for the formation of a solder resist pattern on a printed circuit board which comprises the steps of applying the aforementioned coating composition to a printed circuit board, predrying the coating of the composition thereby imparting hydrophobicity to the coating film, exposing the coating film to an actinic ray, developing the coating film with a dilute aqueous acid solution having only a sparing skin-stimulating property thereby forming a resist pattern therein, and thereafter heating the patterned film thereby thermosetting the formed resist film.
  • a printed circuit board which comprises a printed circuit board having a circuit formed thereon and a resist film made of a cured product of a tertiary amine compound having at least one ethylenically unsaturated bond in the molecule and an epoxy resin and superposed in a prescribed pattern on said printed circuit board.
  • a photo-curable and thermosetting coating composition excellent in resistance to soldering temperature and in electrical insulation and capable of being diluted with water and washed with water can be obtained by combining a tertiary amine compound having at least one ethylenically unsaturated bond in the molecule, a photopolymerization initiator, a diluent, and an epoxy resin as a thermosetting component, provided that the tertiary amine compound is used as neutralized with a carboxylic acid and the epoxy resin is incorporated in the proportion of 2 to 15 equivalents per equivalent of the carboxylic acid to be used for the neutralization, and that the photo-curable and thermosetting coating composition is free from the problems of environmental pollution and fire hazard which are inherent in the conventional liquid photoimageable solder resist.
  • R0 stands for the residue occurring after removal of one tertiary amine from the tertiary amine compound possessing ethylenically unsaturated bond(s)
  • R1 and R2 independently stand for an alkyl group, alkylene group, or alkanol group having 1 to 6 carbon atoms (wherein R1 and R2 may jointly form a cyclic compound or a heterocyclic compound)
  • R3 stands for H, an alkyl group, halogenated alkyl group, alkylene group, or alkanol group having 1 to 6 carbon atoms
  • R4 stands for the residue occurring after removal of one epoxy group from the epoxy resin
  • the portion of the coating which has escaped being photo-crosslinked is rendered soluble in water by the neutralization of the tertiary amine compound in the composition with the dilute aqueous acid solution as shown by the following formula (2) and consequently removed from the substrate.
  • the carboxylic acid used for neutralization is consumed by the epoxy resin and the coating film is consequently vested with hydrophobicity in the step of predrying after application of the composition to the substrate surface. Even when the coating film is left standing after being predried, therefore, it manifests the characteristic feature of avoiding absorption of moisture or loss of tack-free touch of finger.
  • the epoxy resin is contained in the composition in an excess amount relative to the carboxylic acid used for neutralization, the portion of the epoxy resin which survives the reaction with the carboxylic acid used for neutralization is thermally cured with the tertiary amine compound and an optionally added curing agent for epoxy resin in the subsequent heat treatment and the ionic groups do not remain in the thermally cured composition, which avoids entailing the problem of sacrificing such properties as electrical insulation due to absorption of moisture which is inherently suffered by the conventional water-soluble coating composition.
  • the coating composition of this invention therefore, is stable in spite of the inherent ability to be diluted with water.
  • the coating film after being predried excels in such properties as tack-free touch of finger, developing property, photo-curing property, and life.
  • the coating composition of this invention is applied to a printed circuit board, predried, exposed to an actinic ray, and subjected to development and post-curing, the produced solder resist film manifests a conspicuous improvement in resistance to heat and in electrical insulation, the effect never attainable by the conventional water-diluting composition.
  • the solder resist film so produced with the composition of this invention excels in such properties as resistance to soldering temperature, electrical insulation, resistance to electrolytic corrosion, resistance to chemicals, and tightness of adhesion which are required for solder resist.
  • the coating composition of this invention is capable of being diluted with water and the jig which has been used for the application of the composition can be cleaned with tap water.
  • this composition can eliminate such problems of the conventional liquid photoimageable solder resist as pollution of the working environment and exposure of the working environment to fire hazard.
  • a dilute aqueous acid solution such as, for example, an aqueous solution containing lactic acid at a concentration in the range of from 0.5 to 3% by weight or an aqueous solution containing glycolic acid at a concentration in the range of from 0.5 to 3% by weight, which possesses only a meager skin-stimulating property and which, when suffered to adhere to the surface of the coating film at the step of development, is enabled to react with the cured film by the heat treatment can be used.
  • These developing solutions may well be called proper in terms of smell and price.
  • any types of the conventional epoxy resins well known in the art such as bisphenol A type, hydrogenated bisphenol A type, bisphenol F type, bisphenol S type, phenol novolak type, cresol novolak type, and bisphenol A-based novolak type epoxy resins can be used.
  • the polyfuntional epoxy resins such as phenol novolak type, cresol novolak type, and bisphenol A-based novolak type epoxy resins prove to be particularly desirable in view of photo-curing property and resistance to soldering temperature.
  • the secondary amines which are usable for the partial addition to the epoxy groups include such aliphatic secondary amines as dimethylamine, diethylamine, diallylamine, diisopropylamine, diisobutylamine, diethanolamine, morpholine, and piperidine, for example. These secondary amines may be used either singly or in the form of a combination of two or more members. Among other secondary amines cited above, diethanolamine, morpholine, and piperidine prove to be particularly desirable from the viewpoint of ease of reaction.
  • Examples of the monocarboxylic acid having an ethylenically unsaturated bond, which is intended for the reaction with the residual epoxy group include acrylic acid, methacrylic acid, cinnamic acid, and the reaction product of a saturated or unsaturated dibasic acid anhydride with a (meth)acrylate having one hydroxyl group per molecule. These compounds may be used either singly or in the form of a combination of two or more members. Among other monocarboxylic acids cited above, acrylic acid and methacrylic acid prove to be particularly desirable from the standpoint of the photo-curing property.
  • the compounds having at least two ethylenically unsaturated bonds and usable for the sake of the reaction of (B) mentioned above include acrylates such as trimethylolpropane triacrylate, pentaerythritol tetraacrylate, and dipentaerythritol hexaacrylate; such well-known epoxy acrylates of the bisphenol A type, hydrogenated bisphenol A type, bisphenol F type, bisphenol S type, phenol novolak type, cresol novolak type, and bisphenol A-based novolak type; methacrylates or epoxy methacrylates corresponding to the acrylates or epoxy acrylates cited above; and epoxyurethane acrylates resulting from the reaction of an isocyanate group-containing (meth)acrylate [inclusive of the product of half urethanation of a diisocyanate with a hydroxyl group-containing (meth)aclylate] with the epoxy (meth)acrylates mentioned above, for example.
  • acrylates such as tri
  • the secondary amines which are usable for the Michael reaction to said compound having ethylenically unsaturated bonds include such aliphatic secondary amines as dimethylamine, diethylamine, diallylamine, diisopropylamine, diisobutylamine, diethanolamine, morpholine, and piperidine and such secondary amine-containing imidazoles as the products of Shikoku Chemicals Co., Ltd. marketed under registered trademark designation of "CUREZOL" 2MZ, 2E4MZ and C11Z.
  • the glycidyl amine compounds which are usable for the sake of the reaction of (C) mentioned above include N,N-diglycidyl aniline, N,N,N',N'-tetraglycidyl diaminodiphenyl methane, N,N,N',N'-tetraglycidyl-m-xylylene diamine, and N,N,N',N'-tetraglycidyl-1,3-bisaminomethyl cyclohexane, for example.
  • N,N,N',N'-tetraglycidyl-m-xylylene diamine and N,N,N',N'-tetraglycidyl-1,3-bisaminomethyl cyclohexane prove to be particularly desirable from the viewpoint of ease of impartation of water-solubility after neutralization.
  • Examples of the monocarboxylic acid having an ethylenically unsaturated bond which is intended for the reaction with said glycidyl amine compound, include acrylic acid, methacrylic acid, cinnamic acid, and the reaction product of a saturated or unsaturated dibasic acid anhydride with a (meth)acrylate having one hydroxyl group per molecule. These compounds may be used either singly or in the form of a combination of two or more members. Among other monocarboxylic acids cited above, acrylic acid and methacrylic acid prove to be particularly desirable from the viewpoint of the photo-curing property.
  • the tertiary amine compounds having ethylenically unsaturated bond(s) in the molecule and obtained by the reaction of (A) or (B) mentioned above may be used singly or in the form of a combination of two or more members.
  • the compounds which are obtained by the reaction of (C) mentioned above are not easy to use singly because they have low softening points and consequently suffer from inferior tack-free touch of finger.
  • the photosensitive compounds obtained by the reaction of (A) mentioned above are not easily synthesized and acquire stability only with difficulty. In view of all these factors, the synthesis by the reaction of (B) mentioned above proves to be most suitable from the commercial point of view.
  • the amine value of the tertiary amine compound having ethylenically unsaturated bond(s) is desired to fall in the range of from 35 to 150 mg KOH/g, preferably from 50 to 100 mg KOH/g. If the amine value is less than 35 mg KOH/g, tertiary amine compound is not enabled by the neutralization with the carboxylic acid to acquire sufficient solubility in water and is effectively put to use only with difficulty. Conversely, if the amine value exceeds 150 mg KOH/g, there may arise the problem that the composition exhibits low photo-curing property and the cured film to be obtained in the subsequent step suffers from impairment of electrical insulating property.
  • photopolymerization initiators examples include benzoin and alkyl ethers thereof such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; acetophenones such as acetophenone, 2,2-dimethoxy-2-phenyl acetophenone, 2,2-diethoxy-2-phenyl acetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl -1-[4-(methylthio)phenyl]-2-morpholino-propane-1-on, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone; anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butyl anthraquinone, 1-chloroanthraquinone, and 2-amylan
  • photopolymerization initiators may be used either singly or in the form of a combination of two or more members.
  • a photopolymerization initiator may be used in combination with one or more well-known conventional photopolymerization accelerators such as of the benzoic acid type and the tertiary amine type.
  • the amount of the photopolymerization initiator to be used suitably falls in the range of from 1 to 30 parts by weight, preferably from 5 to 25 parts by weight, based on 100 parts by weight of the photosensitive resin component mentioned above. If the amount of the photopolymerization initiator to be used is less than the lower limit of the range mentioned above, the composition will suffer from inferior photo-curing property. Conversely, if the amount exceeds the upper limit of the range, the composition will entail the disadvantage of exhibiting inferior quality for solder resist.
  • water and/or an organic solvent may be used.
  • deionized water which contains no ionic substance proves to be desirable from the standpoint of enabling the composition to enjoy good shelf stability during storage.
  • the amount of the water to be used is desired to be not more than 100 parts by weight, based on 100 parts by weight of the photosensitive resin mentioned above. If the amount of the water to be used exceeds the upper limit mentioned above, though the quality of the composition is not adversely affected, the inevitable decrease in the concentration of the nonvolatile content entails the disadvantage that the efficiency of the application of composition for obtaining a film thickness necessary for solder resist will decrease.
  • organic solvents examples include ketones, cellosolves, carbitols, cellosolve acetates, carbitol acetates, propylene glycol ethers, dipropylene glycol ethers, propylene glycol ether acetates, dipropylene glycol ether acetates, and aromatic hydrocarbons.
  • water-soluble organic solvents prove to be particularly desirable.
  • the amount of the organic solvent to be used is desired to be not more than 50 parts by weight, preferably not more than 30 parts by weight, based on 100 parts by weight of the photosensitive resin mentioned above. If the amount of the organic solvent to be used exceeds the upper limit mentioned above, though the quality of the composition is not adversely affected, the problem of environmental pollution and the problem of fire hazard will be entailed.
  • epoxy resin which serves as a thermosetting component as mentioned above
  • well-known conventional epoxy resins such as bisphenol A type, hydrogenated bisphenol A type, bisphenol F type, bisphenol S type, phenol novolak type, cresol novolak type, bisphenol A-based novolak type, biphenol type, bixylenol type, and N-glycidyl type epoxy resins and glycidyl ethers of polyethylene glycol and polypropylene glycol may be used either singly or in the form of a combination of two or more members. From the viewpoint of the developing property, the epoxy resin to be used is desired to be of the water-soluble or water-dispersion type.
  • the water-soluble epoxy resins include such nonionic water-soluble resins as diglycidyl ethers of polyethylene glycol and polypropylene glycol, for example. They also include the resins produced by adding to a liquid epoxy resin a nonionic or cationic surface-active agent thereby imparting thereto solubility in water such as, for example, the resin "Aqua Tohto 510" (trademark of Tohto Resin Kako K.K.) obtained by adding a surface-active agent to a bisphenol A type epoxy resin.
  • the water-dispersion type epoxy resins include the resins produced by melting solid epoxy resins or dissolving them in a solvent and adding to the resultant liquid a nonionic or cationic surface-active agent such as, for example, the resin "Aqua Tohto 5003" (trademark of Tohto Resin Kako K.K.) obtained by adding a surface-active agent to a novolak type epoxy resin, resins obtained by imparting a self-emulsifying function to solid cresol novolak type epoxy resins such as, for example, a commercial product of Nagase Kasei K.K.
  • powdery epoxy resins sparingly soluble in the diluent mentioned above and dispersible in water such as biphenol type, bixylenol type and bisphenol S type epoxy resins, diglycidyl esters of terephthalic acid, and triglycidyl isocyanurate, for example.
  • powdery epoxy resins which are sparingly soluble in said diluent prove to be particularly desirable from the viewpoint of the tack-free touch of finger which the coating film exhibits in the predried state.
  • the term "sparingly soluble resin” as used herein is to be construed as including resins which are partially soluble in the diluent.
  • the amount of the epoxy resin component to be incorporated in the composition is desired to be in the proportion of 2 to 15 equivalents, preferably 4 to 10 equivalents, per equivalent of the carboxylic acid which has been used for the neutralization of the photosensitive resin component.
  • the epoxy resin in the step of predrying, manifests the effect of imparting hydrophobicity to the coating film by reacting with the carboxylic acid used for the neutralization.
  • the epoxy group is consumed by the carboxylic acid which has been used for the neutralization as described above.
  • the proportion of the epoxy resin component is less than two equivalents per equivalent of the carboxylic acid, therefore, there will ensue the disadvantage that the addition of the carboxylic acid to the epoxy resin molecule is induced as attended by monoepoxidation or epoxyesterification, the three-dimensional crosslinking reaction is prevented from proceeding readily during the thermosetting reaction, and the cured film is precluded from acquiring necessary quality sufficiently. Conversely, if the proportion exceeds 15 equivalents per equivalent of the carboxylic acid, the disadvantage will arise that the concentration of the photosensitive group in the composition is lowered to the extent of degrading the photo-curing property and the resistance to attack by developing solution.
  • the part of the epoxy group which survives the reaction of the epoxy resin component with the carboxylic acid used for the neutralization is thermally cured with the tertiary amine compound having ethylenically unsaturated bond(s) in the molecule or an optionally added latent curing agent for epoxy resin such as, for example, an imidazole, dicyandiamide, or boron trifluoride monoethylamine complex.
  • an optionally added latent curing agent for epoxy resin such as, for example, an imidazole, dicyandiamide, or boron trifluoride monoethylamine complex.
  • the carboxylic acids which are effectively usable herein for the purpose of neutralizing the tertiary amine compound possessing ethylenically unsaturated bond(s) in the molecule include monocarboxylic acids such as formic acid, acetic acid, propionic acid, acrylic acid, glycolic acid, and lactic acid and dicarboxylic acids such as L-glutamic acid, for example.
  • monocarboxylic acids prove to be particularly desirable in terms of liquid stability of the product of neutralization, ease of impartation of solubility in water, and developing property after the predrying. From the standpoint of smell, such hydroxycarboxylic acids as lactic acid and glycolic acid which have high boiling points and low levels of volatility prove to be particularly desirable.
  • these carboxylic acids are enabled by a heat treatment to react efficiently with the epoxy resin mentioned above to the extent of being deprived of ionicity and giving rise to electrical insulation required for solder resist.
  • the amount of the carboxylic acid to be added is desired to be in the proportion of 0.8 to 2.0 equivalents, preferably 1.0 to 1.4 equivalents, per equivalent of the amine contained in the tertiary amine compound possessing ethylenically unsaturated bond(s) in the molecule. If the amount of the carboxylic acid to be added is less than the lower limit of the range mentioned above, there will ensue the disadvantage that the concentration of the hydrophilic quaternary ammonium salt to be formed by the neutralization is too low to allow impartation of solubility in water.
  • the neutralization of the tertiary amine compound with the carboxylic acid mentioned above may be accomplished by either having the tertiary amine compound preparatorily neutralized with the carboxylic acid and adding the resultant product of neutralization to the photo-sensitive resin composition or adding the carboxylic acid to the photosensitive resin composition containing the tertiary amine compound, the photopolymerization initiator, and the diluent during the preparation of this photosensitive resin composition.
  • the photo-curable and thermosetting coating composition of this invention which is obtained as described above and can be diluted with water may optionally incorporate therein additionally a photopolymerizable monomer.
  • the photopolymerizable monomers which are usable herein include hydroxyl group-containing acrylates such as 2-hydroxyethyl acrylate, 2-hydroxybutyl acrylate, pentaerythritol triacrylate, and dipentaerythritol pentacrylate; acrylamide derivatives such as acrylamide and N-methylolacrylamide; water-soluble acrylates such as polyethylene glycol diacrylate and polypropylene glycol diacrylate; acrylates such as trimethylolpropane triacrylate and pentaerythritol tetraacrylate; and methacrylates corresponding to the acrylates mentioned above, for example.
  • photopolymerizable monomers may be used either singly or in the form of a combination of two or more members in an amount incapable of causing the problem of dry tack.
  • the hydrophilic group-containing (meth)acrylates prove to be particularly desirable in terms of liquid stability of the composition and the polyfunctional (meth)acrylates prove to be particularly desirable in terms of the photo-curing property.
  • macromolecular compounds as polyvinyl alcohol, polyacrylamide, carboxymethyl cellulose, polyvinyl formal resin, and polyvinyl acetal resin which are water-soluble resins can be used as a protective colloid. The use of the protective colloid is effective in improving the liquid stability of the composition.
  • a surface-active agent may be used.
  • the surface-active agent is desired to be of a nonionic type having an HLB (hydrophilic-lipophilic balance) value of not less than 13.
  • such well known and widely used inorganic fillers as barium sulfate, talc, and silica can be used for the purpose of enhancing the characteristic properties of the composition of this invention such as adhesion, hardness, and resistance to soldering temperature.
  • the amount of the inorganic filler to be used is desired to be in the range of not more than 100 parts by weight, preferably 5 to 50 parts by weight, based on 100 parts by weight of the photosensitive resin component mentioned above.
  • well known and widely used additives such as color pigments, thermopolymerization inhibitors, thickening agents, anti-foaming agents, leveling agents, and coupling agents may be used, as occasion demands.
  • the coating composition of this invention may further incorporate therein, when necessary, other thermosetting resins such as melamine resin, blocked isocyanate, or oxazoline resin in an amount incapable of impairing the developing property thereof.
  • other thermosetting resins such as melamine resin, blocked isocyanate, or oxazoline resin in an amount incapable of impairing the developing property thereof.
  • the composition allows use of such a compound as adenine, vinyl triazine, dicyandiamide, orthotolyl biguanide, or melamine, for example.
  • the amount of this compound to be used is desired to be not more than 20 parts by weight, based on 100 parts by weight of the photosensitive resin mentioned above.
  • the addition of this compound is effective in enhancing the resistance of the composition to chemicals.
  • the liquid coating composition which is prepared as described above and which is consequently enabled to be diluted with water and washed with water is adjusted, when necessary by dilution with water, to a level of viscosity fit for the coating method, applied by the technique of screen printing, curtain coating, spray coating, or roll coating to a printed circuit board having a circuit already formed thereon, and then predried at a temperature in the range of from 60 to 100°C, for example, thereby to impart hydrophobicity to the coating and evaporate the organic solvent and water from the coating and give rise to a tack-free coating film.
  • the composition coated on the printed circuit board is selectively exposed to an actinic ray through a photomask having a prescribed pattern and the composition in the unexposed parts of the coating film is developed with a dilute aqueous acid solution to obtain a resist pattern.
  • the acid which has been consumed at the step of said predrying is replenished with the dilute aqueous acid solution which is used as the developing solution in the process of development.
  • the coating film can be endowed with hydrophilicity and the unexposed parts which have not undergone photo-crosslinking can be removed.
  • inorganic acids such as hydrochloric acid and nitric acid
  • carboxylic acids such as acetic acid, formic acid, propionic acid, lactic acid, and glycolic acid
  • sulfonic acids such as p-toluene sulfonic acid
  • acidic phosphoric esters can be used.
  • carboxylic acids prove to be particularly desirable in respect that even when they adhere to the surface of a photo-cured coating film, they are deprived of ionicity owing to their reaction with the epoxy group.
  • the concentration of the acid in the dilute aqueous acid solution is desired to be in the range of from 0.5 to 3% by weight in terms of the solubility of the composition in unexposed areas and the resistance of the photo-cured coating film to the attack by developing solution.
  • the photo-cured coating film is further thermally cured by subjecting to the heat treatment at a temperature in the range of from 140 to 180°C, for example, to form a solder resist film which excels in adhesion, hardness, resistance to soldering temperature, resistance to chemicals, resistance to solvents, electrical insulation, and resistance to electrolytic corrosion.
  • the light sources which are advantageously used for the purpose of photo-curing of the composition include low-pressure mercury lamp, medium-pressure mercury lamp, high-pressure mercury lamp, ultra-high-pressure mercury lamp, xenon lamp, and metal halide lamp, for example.
  • the laser beam can be utilized as the actinic ray for exposure of the film. Besides them, electron beam, ⁇ ray, ⁇ ray, ⁇ ray, X ray, and neutron ray are likewise usable.
  • A-1 varnish a photosensitive resinous solution having a nonvolatile content of 64% and an amine value of the solid content of 62 mg KOH/g
  • the photosensitive resinous solution consequently obtained (hereinafter referred to as "B-1 varnish") was found to have a nonvolatile content of 66% and an amine value (as reduced to solid content) of 57 mg KOH/g.
  • reaction product and 35 parts of diethanolamine and 5.5 parts of 2E4MZ (a secondary amine-containing imidazole derivative produced by Shikoku Kasei K.K.) gradually added dropwise thereto were left undergoing a Michael reaction at 65 to 75°C for four hours.
  • the photosensitive resinous solution thus obtained (hereinafter referred to as "B-2 varnish") was found to have a nonvolatile content of 67% and an amine value of the solid content of 48 mg KOH/g.
  • B-3 compound The reaction product thus obtained (hereinafter referred to as "B-3 compound”) was found to have an amine value of 84 mg KOH/g.
  • A-1 varnish 50 parts Lactic acid 3.3 parts Photopolymerization initiator (product of Chiba-Geigy marketed under trademark designation of "IRGACURE 651”) 4 parts Dipentaerythritol hexaacrylate 3 parts N,N'-methylene-bis-acrylamide 1 part 2PHZ 0.8 part Dicyandiamide 0.2 part Barium sulfate 30 parts Phthalocyanine green 0.7 part Dimethyl polysiloxane (silicone type anti-foaming agent) 1 part Finely divided silica 2 parts Deionized water 4 parts Total: 100 parts
  • H-1 water-soluble epoxy resin composition
  • Bisphenol A type epoxy resin product of Tohto Resin Kako K.K. marketed under trademark designation of "Aqua Tohto 510”
  • Triglycidyl isocyanurate 60 parts
  • Carbitol acetate 10 parts
  • Deionized water 10 parts Total: 100 parts
  • R-1 and H-1 prepared as described above were mixed in the following ratio to obtain a photo-curable and thermosetting coating composition capable of being diluted with water.
  • B-1 varnish obtained in Synthetic Example 2 were kneaded with a three-roll mill to prepare a photosensitive resin composition (hereinafter referred to as "R-2 base").
  • B-1 varnish 50 parts IRGACURE 651 4 parts Pentaerythritol triacrylate 3 parts N,N'-methylene-bis-acrylamide 3 parts 2PHZ 1.5 parts Phthalocyanine green 0.5 part Dimethyl polysiloxane (silicone type anti-foaming agent) 1 part Silica 30 parts Total: 93 parts
  • R-2 base obtained as described above lactic acid in the proportion of 1.2 equivalent per equivalent of the amine contained in said resin composition
  • a water-soluble photosensitive resin composition comprising the following components (hereinafter referred to as "R-2") was prepared.
  • R-2 base 93 parts Lactic acid 3.6 parts
  • a cross-linking agent for the water-soluble photosensitive resin As a cross-linking agent for the water-soluble photosensitive resin, the following components including a water-dispersion type epoxy resin (product of Tohto Resin Kako K.K. marketed under trademark designation of "Aqua Tohto 5003", nonvolatile content; 55%, epoxy equivalent of solid content; 205) and a powdery epoxy resin were stirred and dispersed with a homogenizer, to prepare a water-dispersion type epoxy resin composition (hereinafter referred to as "H-2").
  • Aqua Tohto 5003 50 parts Triglycidyl isocyanurate 40 parts Polyvinyl acetal resin (product of Sekisui Chemical Co., Ltd. marketed under product code of "S-LEC KW-1”) 8 parts Finely divided silica 2 parts Total: 100 parts
  • R-2 and H-2 prepared as described above were mixed at the following ratio, to obtain a photo-curable and thermosetting coating composition capable of being diluted with water.
  • B-2 varnish and B-3 compound obtained in Synthetic Examples 3 and 4 were kneaded with a three-roll mill to prepare a water-soluble photosensitive resin composition (hereinafter referred to as "R-3").
  • R-3 water-soluble photosensitive resin composition
  • H-3 water-soluble epoxy resin composition
  • Melamine resin product of Sanwa Chemicals Co., Ltd. marketed under product code of "NIKALAC MW-30”
  • Water-dispersion type cresol novolak epoxy resin product of Nagase Kasei K.K.
  • R-3 and H-3 prepared as described above were mixed in the following ratio, to obtain a photo-curable and thermosetting coating composition capable of being diluted with water.
  • compositions obtained in the working examples and the comparative experiment cited above was applied by a screen printing method onto the entire surface of copper-clad substrate having a prescribed pattern formed in advance thereon and then predried at 80°C for periods graduated at an interval of 5 minutes.
  • the coating films consequently formed on the substrates were exposed to an actinic ray according to a solder resist pattern through a negative film tightly superposed thereon. They were then developed with an aqueous 1 wt% lactic acid solution to test for life (the longest predrying period allowing effective development).
  • each of the compositions obtained in the working examples and the comparative experiment cited above was applied by the screen printing method onto the entire surface of copper-clad substrate having a prescribed pattern formed in advance thereon and then predried at 80°C for 30 minutes.
  • the coating films on the substrates were exposed to an actinic ray according to a solder resist pattern through a negative film tightly superposed thereon and then developed with an aqueous 1 wt% lactic acid solution to form a resist pattern thereon.
  • the coating films on the substrates were thermally cured at 150°C for 30 minutes to prepare sample substrates, which were used for evaluation of the following properties.
  • This property was determined by coating a sample substrate with a rosin-based flux, immersing the coated sample substrate for 30 seconds in a solder bath set in advance at 260°C, rinsing the sample with trichloroethane thereby removing the flux therefrom, and visually examining the sample to find the extents of swelling, separation, and discoloration consequently produced in the resist layer on the sample substrate. These phenomena were rated on the following three-point scale.
  • This property was determined by preparing a sample substrate under the conditions mentioned above using a comb type electrode B coupon of IPC B-25, applying a bias voltage of DC 500 V to the comb type electrode, and measuring the initial insulation resistance.
  • This sample substrate was left standing for 200 hours in a thermo-hygrostat kept at 40°C and 95% R.H. After humidification, the sample substrate was tested for insulation resistance in the same manner as described above.
  • compositions obtained in the working examples and the comparative experiment cited above were evaluated for storage stability as follows.
  • a given composition was left standing in a constant-temperature bath at 20°C for one month and then visually examined to find the extents of change in property and in viscosity and evaluate stability during storage.
  • the stability was rated on the following three-point scale.
  • This property was determined by diluting a given composition with deionized water to 2 poises, stirring and mixing the diluted composition, allowing the composition to stand at rest at normal room temperature for one day, and visually examining the diluted composition to find the extents of change in property and in viscosity, thereby evaluating the ability of the composition to be diluted with water. The property was rated on the following three-point scale.
  • a sample substrate was obtained by diluting a given composition to 2 poises as described above, applying the diluted composition by the spray coating method to a copper-clad substrate having a prescribed pattern formed in advance thereon, predrying the coating on the substrate at 80°C for 30 minutes thereby obtaining a tack-free coating film.
  • the coating film on the substrate was exposed to UV rays according to a solder resist pattern through a negative film superposed tightly thereon, developed with an aqueous 1 wt% lactic acid solution thereby forming a resist pattern, and then thermally cured at 150°C for 30 minutes to prepare a sample substrate.
  • the sample substrate was evaluated for resistance to soldering temperature, resistance to acids, and insulation resistance as described above. Then, the sample substrate used for this evaluation was compared with the sample substrate prepared by the screen printing to determine the presence or absence of a degradation of characteristic properties.

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)
  • Epoxy Resins (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
EP19930108973 1992-06-05 1993-06-04 Foto- und wärmehärtende Beschichtungszusammensetzung und Verfahren zum Herstellen von Resist-Lötmasken Expired - Lifetime EP0573053B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP16998592A JPH05343837A (ja) 1992-06-05 1992-06-05 ソルダーレジストインキ組成物及びソルダーレジストパターン形成方法
JP169985/92 1992-06-05

Publications (2)

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EP0573053A1 true EP0573053A1 (de) 1993-12-08
EP0573053B1 EP0573053B1 (de) 1995-10-18

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JP (1) JPH05343837A (de)
DE (1) DE69300657T2 (de)
HK (1) HK1000971A1 (de)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0735426A1 (de) * 1995-03-27 1996-10-02 Dainippon Ink And Chemicals, Inc. Strahlungshärtbare Polymere und Verfahren zu ihrer Herstellung
US6713587B2 (en) 2001-03-08 2004-03-30 Ppg Industries Ohio, Inc. Electrodepositable dielectric coating compositions and methods related thereto
US6824959B2 (en) 2002-06-27 2004-11-30 Ppg Industries Ohio, Inc. Process for creating holes in polymeric substrates
US6951707B2 (en) 2001-03-08 2005-10-04 Ppg Industries Ohio, Inc. Process for creating vias for circuit assemblies
US7000313B2 (en) 2001-03-08 2006-02-21 Ppg Industries Ohio, Inc. Process for fabricating circuit assemblies using electrodepositable dielectric coating compositions
US7002081B2 (en) 2002-06-27 2006-02-21 Ppg Industries Ohio, Inc. Single or multi-layer printed circuit board with recessed or extended breakaway tabs and method of manufacture thereof

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3944027B2 (ja) * 2001-11-16 2007-07-11 三井金属鉱業株式会社 フレキシブルプリント配線板の製造方法及びその製造方法で得られたフレキシブルプリント配線板
JP2017003911A (ja) * 2015-06-15 2017-01-05 株式会社ムラカミ 感光性樹脂組成物、感光性フィルム、スクリーン印刷用版材および感光性レジストフィルム

Citations (3)

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Publication number Priority date Publication date Assignee Title
DE3841422A1 (de) * 1987-12-08 1989-06-22 Kansai Paint Co Ltd Verfahren zur bildung eines ausgehaerteten beschichtungsfilmes
EP0323563A2 (de) * 1987-11-30 1989-07-12 Taiyo Ink Manufacturing Co. Ltd. Lichtempfindliche wärmehärtbare Harzzusammensetzung und Methode zur Herstellung von Lötstoppmasken damit
EP0469537A2 (de) * 1990-08-02 1992-02-05 Ppg Industries, Inc. Lichtempfindliche, elektroabscheidbare Photoresistzusammensetzung

Patent Citations (3)

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Publication number Priority date Publication date Assignee Title
EP0323563A2 (de) * 1987-11-30 1989-07-12 Taiyo Ink Manufacturing Co. Ltd. Lichtempfindliche wärmehärtbare Harzzusammensetzung und Methode zur Herstellung von Lötstoppmasken damit
DE3841422A1 (de) * 1987-12-08 1989-06-22 Kansai Paint Co Ltd Verfahren zur bildung eines ausgehaerteten beschichtungsfilmes
EP0469537A2 (de) * 1990-08-02 1992-02-05 Ppg Industries, Inc. Lichtempfindliche, elektroabscheidbare Photoresistzusammensetzung

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0735426A1 (de) * 1995-03-27 1996-10-02 Dainippon Ink And Chemicals, Inc. Strahlungshärtbare Polymere und Verfahren zu ihrer Herstellung
US5847022A (en) * 1995-03-27 1998-12-08 Dainippon Ink And Chemicals, Inc. Radiation curable resin composition and method therefor
CN1087442C (zh) * 1995-03-27 2002-07-10 大日本油墨化学工业株式会社 能量射线硬化型树脂组合物及其制法
US6713587B2 (en) 2001-03-08 2004-03-30 Ppg Industries Ohio, Inc. Electrodepositable dielectric coating compositions and methods related thereto
US6951707B2 (en) 2001-03-08 2005-10-04 Ppg Industries Ohio, Inc. Process for creating vias for circuit assemblies
US7000313B2 (en) 2001-03-08 2006-02-21 Ppg Industries Ohio, Inc. Process for fabricating circuit assemblies using electrodepositable dielectric coating compositions
US6824959B2 (en) 2002-06-27 2004-11-30 Ppg Industries Ohio, Inc. Process for creating holes in polymeric substrates
US7002081B2 (en) 2002-06-27 2006-02-21 Ppg Industries Ohio, Inc. Single or multi-layer printed circuit board with recessed or extended breakaway tabs and method of manufacture thereof
US7159308B2 (en) 2002-06-27 2007-01-09 Ppg Industries Ohio, Inc. Method of making a circuit board

Also Published As

Publication number Publication date
JPH05343837A (ja) 1993-12-24
DE69300657D1 (de) 1995-11-23
EP0573053B1 (de) 1995-10-18
HK1000971A1 (en) 1998-05-15
DE69300657T2 (de) 1996-03-21

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